Method of using molybdenum carbide catalyst

ABSTRACT

A molybdenum carbide compound is formed by reacting a molybdate with a mixture of hydrogen and carbon monoxide. By heating the molybdate powder from a temperature below 300° C. to maximum temperature 850° C., a controlled reaction can be conducted wherein molybdenum carbide is formed. A high surface area, nanograin, metastable molybdenum carbide can be formed when the reaction temperature is below 750° C. The metastable molybdenum carbide is particularly suitable for use as a catalyst for the methane dry reforming reaction and the water gas shift reaction.

RELATED APPLICATION

[0001] This application is a divisional application of U.S. patentapplication Ser. No. 09/817,523, filed on Mar. 26, 2001. The entiredisclosure of this application is incorporated herein by reference.

BACKGROUND OF THE INVENTION

[0002] Synthesis gas is a mixture of hydrogen and carbon monoxide, whichis formed from methane reforming and has a variety of differentapplications in organic reactions. This can be formed by combining steamand oxygen with methane at high temperatures. Another method of formingsynthesis gas from methane is the methane dry reforming reaction. Inthis reaction, carbon dioxide is mixed with methane and the blend issubjected to high temperature i.e., 850° C. in the presence of acatalyst. This in turn forms hydrogen and carbon monoxide. The hydrogenfrom the reforming process is particularly suitable for use in fuel cellpower systems.

[0003] The typical catalyst for use in the methane dry reformingreaction is a noble metal such as gold, platinum or the like. However,these catalysts tend to be relatively expensive. Molybdenum carbide isknown as a catalyst for such reaction. However, this can be difficult toform. Further for use as a catalyst, high surface area is critical.Molybdenum carbide tends to form larger grains having reduced surfaceareas which in turn reduces its effectiveness as a catalyst. Thus,because of this problem and the high temperature and time required toform molybdenum carbide, it has not been used commercially as a catalystfor the methane dry reforming reaction.

[0004] Synthesis gas, mainly a mixture of H₂ and CO, may also containCO₂, can be a cheap and easy to obtain fuel for fuel cells. However, COin the synthesis gas can poison the expensive fuel cell catalyst.Therefore, it has to be removed from the synthesis gas before the gas isused for fuel cells. Low temperature water gas shift (WGS) reactionconverts CO into CO₂, a harmless gas for the fuel cell catalyst.Additional benefit from the low temperature WGS is that it alsogenerates H₂. It can be seen that WGS reaction could have a significantpotential in the fuel cell technology.

SUMMARY OF THE INVENTION

[0005] The present invention is premised on the realization that amolybdenum carbide catalyst suitable for use in the methane dryreforming reaction as well as other reactions can be formed atrelatively low temperatures and in relatively short periods of time.These reactions also include fuel processing as applicable in fuel celluses.

[0006] More particularly the present invention is premised on therealization that molybdates such as ammonium molybdate can be directlyformed into a high surface area molybdenum carbide by direct reactionwith a mixture of hydrogen and carbon monoxide and methane. Themolybdate is heated from a temperature below 300° C. to a temperaturebelow 850° C. at a ramp rate of about 0.5-20° C./min in the presence ofthe hydrogen, carbon monoxide mixture and methane. This permits themolybdate to be reduced and then carburized directly to molybdenumcarbide.

[0007] Depending on the reduction/carburization gases and the heatingprofile used, the product powders can have a wide range of specificsurface area from just over 30 m²/g to almost 100 m²/g. Typically, a 35m²/g Mo₂C powder can be generated with CO/H₂ mixture and a highersurface area powder with a combination of CO/H₂ and CH₄/H₂ mixtures. Atwo-step process was used to generate Mo₂C powders with surface areaover 60 m²/g. First, the precursor was soaked in a CO/H₂ mixture at alow temperature (300°-400° C.). Then, the intermediate was heated-upslowly in the CO/H₂ mixture (up to 500° C.) and a CH₄/H₂ mixture (above500° C.) to the final soak temperature (600°-650° C.). It is believedthat Mo₂C starts to nucleate during the low temperature soak and theintermediate (XRD amorphous) from the soak develop slowly into Mo₂Cduring the ramp and the high temperature soak. It is this lowtemperature nucleation give the finished powder very high surface area.CO was selected as the low temperature carburization gas because it ismore active than CH₄ at low temperatures, while CH₄ is a better choiceat higher temperatures.

[0008] The high surface Mo₂C is useful as a catalyst in the methane dryreforming reaction.

[0009] The high surface area Mo₂C powder of the present invention canhave higher catalysis activity for the WGS reaction than the commercialcatalyst, which is widely used currently. Generally, the higher thesurface area of a Mo₂C powder, the higher the catalysis activity thepowder can deliver.

DETAILED DESCRIPTION

[0010] According to the present invention, a molybdenum carbide powderis formed from a molybdate or molybdenum oxide by reacting it under 750°C. with a mixture of a reducing and carburizing gases, which arespecifically hydrogen and carbon monoxide and methane. The formedcarbide has a structure of Mo₂C_(y), wherein y represents 0.95 to 1.05.

[0011] The starting molybdate can be any molybdate wherein the counterion is not a metal. Generally, the counter ion will be an organiccompound or ammonium which is preferred due to its availability. Othermolybdenum compounds such as molybdenum oxides can also be used.

[0012] The reaction gas is a blend of hydrogen and carbon monoxide ormethane at a ratio between 3:1 to 1:1 and preferably at 1:1 ratio (byvolume). Other carburizing gases such as ethylene can also be used.

[0013] The reaction can be conducted in any suitable furnace whichpermits control of the gaseous atmosphere and temperature. A rotary kilnis particularly suitable due to its ability to ensure adequate mixing ofthe solid and gaseous reactants. The ammonium molybdate or molybdenumoxide powder is simply loaded into a quartz liner and placed into therotary kiln.

[0014] The system is purged with nitrogen first and then a hydrogen,carbon monoxide mixture in the ratio stated above (preferably 30-50% CO)is introduced. The temperature can be quickly raised to 300° C.-400° C.and held for 1-5 hours and thereafter the temperature ramp rate shouldnot exceed 20° C./min and preferably is 0.5-20° C./min. The reactiontemperature and the furnace temperature ramp rate are critical forachieving maximum surface area. The molybdate starts decomposition atabout 300° C. It decomposes into oxides, which at some stage can beamorphous. The reduction and carburization of the resulting oxide occursat the same time when the temperature goes above 400° C. A second 3- to5-hour soak (in H/CH₄ with the above stated ratio preferably 20-60% CH₄)at a temperature between 550° to 850° C. provides enough time toexpedite the formation of molybdenum carbide.

[0015] The maximum temperature should not exceed 850° C. and mostpreferably be less than 700° C. At 700° C., the reaction can becompleted in 2 to 4 hours. The reaction time can be shortened byincreasing the reaction temperature at the expense of increasing grainsize and reducing surface area.

[0016] During the reaction, the feeding gas composition can be changedif desired in order to adjust the total carbon content of the powder.Subsequently, the reactor is cooled down with flowing hydrogen, carbonmonoxide mixture, hydrogen alone, or nitrogen. Because of the highsurface area, the powder should be passivated with diluted oxygen or airafter the powder cools down to room temperature.

[0017] The molybdenum carbide formed in this manner is a metastableMo₂C_(y). X-ray diffraction on the carbide powder shows some missingpeaks in the diffraction pattern. At this stage, the powder samplesexhibit specific surface areas of over 35 m²/g.

[0018] High surface area Mo₂C has also been used as a catalyst for a lowtemperature water gas shift (WGS) reaction, from which H₂ and CO₂ aregenerated from CO and H₂O (vapor). As we know, synthesis gas (mainly amixture of H₂ and CO, may also contain CO₂) can be a cheap and easy toobtain (from cracking of many organic compounds) fuel for fuel cells.However, CO in the synthesis gas can poison the expensive fuel cellcatalyst. Therefore, it has to be removed from the synthesis gas beforethe gas is used for fuel cells. Low temperature WGS reaction converts COinto CO₂, a harmless gas for the fuel cell catalyst. Additional benefitfrom the low temperature WGS is that it also generates H₂. It can beseen that WGS reaction can have a significant potential in the fuel celltechnology. Our preliminary test result indicates that a high surfacearea Mo₂C powder can have higher catalysis activity for WGS reactionthan the commercial Cu—Zn catalyst, which is widely used currently.Generally, the higher the surface area of a Mo₂C powder, the higher thecatalysis activity the powder can deliver.

[0019] The invention will be further appreciated in light of thefollowing detailed examples.

EXAMPLE 1

[0020] 1.0 lb of ammonium molybdate powder was loaded in a rotary kilnand heated to 590° C. and then 760° C. at a ramp rate of about 10°C./min in a gaseous mixture of H₂ and CO at 1:1 volume ratio. The soaktime is 5 hours at 590° C. and 3 hours at 760° C. After the furnacecooled down to room temperature, the powder was passivated with a diluteair for about 1 hour. XRD on the product powder shows Mo₂C. The BETspecific surface area of the powder was 18.5 m²/g. Carbon analysis onthe powder showed 5.84% combined carbon and 1.72% free carbon.

EXAMPLE 2

[0021] 1.0 lb of ammonium molybdate powder was loaded in a rotary kilnand heated to 590° C. and then 700° C. at a ramp rate of about 10°C./min in a gaseous mixture of H₂ and CO at 1:1 volume ratio. The soaktime is 5 hours at 590° C. and 3 hours at 700° C. After the furnacecooled down to room temperature, the powder was passivated with a diluteair for about 1 hour. XRD on the product powder shows defect Mo₂C withsome missing peaks in the XRD pattern. The BET specific surface area ofthe powder was 37.7 m²/g. Carbon analysis on the powder showed 6.07%combined carbon and 1.62% free carbon.

EXAMPLE 3

[0022] 1.0 lb of ammonium molybdate powder was loaded in a rotary kilnand heated to 700° C. at a ramp rate of about 10° C./min in a gaseousmixture of H₂ and CO at 1:1 volume ratio. The soak time is 5 hours at700° C. After the furnace cooled down to room temperature, the powderwas passivated with a dilute air for about 1 hour. XRD on the productpowder shows defect Mo₂C with some missing peaks in the XRD pattern. TheBET specific surface area of the powder was 35.7 m²/g. Carbon analysison the powder showed 5.99% combined carbon and 2.15% free carbon.

EXAMPLE 4

[0023] 1.6 lb of ammonium molybdate powder was loaded in a productiontube furnace and heated to 1080° F. (582° C.) and then 1290° F. (699°C.) at a ramp rate of about 8° C./min in a gaseous mixture of H₂ and COat 3:1 volume ratio. The soak time is 10 hours at 1080° F. and 3 hoursat 1290° F. After 3 hours carburization at 1290° F., additional 16% CO₂was introduced for free carbon removal. The decarburization wasperformed for another 3 hours. After the furnace cooled down in N₂ toroom temperature, the powder was passivated with a dilute air. XRD onthe product powder showed Mo₂C and a XRD peak broadening technique gavea Mo₂C grain size of 26 nm. The BET specific surface area of the powderwas 39 m²/g. Carbon analysis on the powder showed 5.53% combined carbonand <0.04% free carbon.

EXAMPLE 5

[0024] A methane dry reforming catalyst test was done on the metastableMo₂C powder synthesized as shown in example 2. The test was performed ina small tube furnace at 850° C. Two quartz wool plugs were used to keep5 g Mo₂C powder layer in between and permit the reacting gases passingthrough. Mass flow meters were used to control the gas flow and a3-channel (CH₄/CO/CO₂) IR analyzer was used to monitor the inlet andoutlet gas compositions. The test showed 47% CO yield initially, whichis very close to the equilibrium 49% CO yield. This high CO yield waskept for over 48 hours. Then, the yield dropped to and stabilized atabout 25% for another 24 hours. The test was interrupted after 72 hours.Catalytic activity was still obvious, even after 72 hours of reaction.

[0025] Other than the surface area, the surface status of a Mo₂C powderdirectly affects its catalysis activity. It is known that the freecarbon deposit on the powder surface can block some active sites andlower the catalysis activity of the powder. The surface oxygen alsoaffects the catalysis activity. As indicated, due to the highly activenature of a high surface area Mo₂C powder, a passivation treatment isgenerally necessary after the powder synthesis and before the exposureof the powder to air. During the passivation treatment, awell-controlled oxidation (0.01 to 0.1% O₂ in N₂) is applied to thepowder so that a very thin and dense layer of oxide forms on the surfaceof the powder preventing the powder from further oxidation. An XPSanalysis on a passivated Mo₂C powder has confirmed the existence ofMolybdenum oxide on the surface of the powder.

[0026] This oxide layer has to be removed before any catalysis test. Atreatment was done on the Mo₂C powder right before the WGS catalysistest. The treatment comprises of 1 - or 2-hour annealing of the powderat 300°-600° C. in flowing H₂ or a CH₄/H₂ mixture. This treatmentsignificantly increases the catalysis activity.

[0027] Even though a Mo₂C powder is quite stable in the WGS feeding gasstream at temperatures below 500° C., it may still be a partiallyoxidized after a long term exposure to the feeding gas. Therefore,recovery capability is an important property of this catalyst. Testresults indicate that a high surface area Mo₂C can be recovered in-situwith a re-carburization treatment. The re-carburization treated powdercan have a high WGS catalysis activity again.

[0028] More details of the work is illustrated in the followingexamples.

EXAMPLE 6

[0029] 5 g ammonium molybdate powder was loaded in a tube furnace. Inthe gas stream of 50%CO with H₂, the powder was heated-up 350° C. andsoaked at 350° C. for 2 hours. The powder was then ramped at 1° C./minin 50% CO with H₂ to 500° C. and then in 40% CH₄ with H₂ to 620° C.After reaching 620° C., the powder was soaked in 40% CH₄ with H₂ at 620°C. for 4 hours. The product powder was Mo₂C as confirmed by XRD and theBET surface area of the powder was 90 m²/g. The powder contains no freecarbon (<0.04%).

EXAMPLE 7

[0030] 5 g of a Mo₂C powder with a specific surface area 54 m²/g wasused as a catalyst for the WGS test. The feeding gas had 49.0% H₂, 6.0%CO, 15.0% CO₂ and 30.0% H₂O (vapor) with the total flow rate about 1540cc/min, or 1330 min⁻¹ space velocity (assuming Mo₂C has bulk density 4.5g/cc). IR was used for the inlet and outlet gas composition analysis andthe magnitude of CO loss or CO₂ gain after the WGS reaction was used tomeasure the WGS catalysis activity of the catalyst. At 250° C., themaximum CO loss was 0.30 μmol/g.sec and the corresponding CO₂ gain was0.75 μmol/g.sec. As a comparison, a commercial Cu—Zn catalyst gave 6.11μmol/g.sec CO loss and 5.67 μmol/g.sec corresponding CO₂ gain.

EXAMPLE 8

[0031] 5 g of the same Mo₂C powder as what in the Example 7 was used forthe WGS test. Testing conditions were the same as that in the Example 7.However, a 2-hour annealing at 550° C. in flowing H₂ was done to thepowder right before the WGS test. At 250° C., the powder gave 6.11μmol/g.sec. Maximum CO loss and 5.67 mol/g.sec. corresponding CO₂ gain.

EXAMPLE 9

[0032] 5 g of the same Mo₂C powder as that in the Example 7 was used forthe WGS test. Testing conditions were the same as that in the Example 7.However, a 2-hour annealing at 550° C. in flowing H₂ and 10% CH₄ gasmixture was done to the powder right before the WGS test. At 250° C.,the powder gave 5.97 μmol/g.sec. maximum CO and 5.70 mol/g.seccorresponding CO₂ gain.

EXAMPLE 10

[0033] 5 g of a Mo₂C powder with a specific surface area 77 m²/g wasused for the WGS test. Testing conditions were the same as that in theExample 7. A 2-hour annealing at 550° C. in flowing H₂ and 10% CH₄ gasmixture was done to the powder right before the WGS test. At 250° C.,the powder gave 9.77 μmol/g.sec. maximum CO loss and 7.89 μmol/g.sec.corresponding CO₂ gain.

[0034] For easier comparison, the 250° C. WGS test results from theExamples 7-10 are summarized in the following table. Catalyst Cu—ZnOMo₂C Mo₂C Mo₂C Mo₂C Surface Area — 54 54 54 77 (m²/g) Pre-WGS — — 550°C. in 550° C. in 550° C. in Treatment H₂ 10% 10% CH₄/H₂ CH₄/H₂ CO gain−6.11 −0.30 −4.21 −5.97 −9.77 (μmol/g. sec) CO₂ gain 5.67 0.75 3.33 5.707.89 (μmol/g. sec)

[0035] It can be seen that without any pre-WGS treatment, the 54 m²/gMo₂C powder has little WGS catalysis activity. With some in-situtreatment (better with CH₄/H₂ mixture) right before the WGS testing, the54 m²/g Mo²C powder can have similar WGS catalysis activity as thecommercial Cu—Zn catalyst. The 77 m²/g Mo₂C powder has much higher WGScatalysis activity than the commercial catalyst.

EXAMPLE 11

[0036] 3 g of a partially oxidized Mo₂C powder was used for a recoveringtest. The powder was obtained by exposing the same Mo₂C powder as thatin the Example 6 to a flowing water vapor stream at 600° C. for 1 hour.XRD confirmed the existence of MoO₂ in addition to Mo₂C in the powder.The recovering test started with a 1 -hour WGS test at 250° C. followedby a 30-hour re-carburization treatment with a CH₄/H₂ mixture at 500° C.Then another 1-hour WGS test was done at 250° C. on the re-carburizationtreated powder. The WGS testing conditions were the same as that in theEXAMPLE 2. Before the re-carburization treatment, the powder gave 0.12μmol/g.sec. maximum CO loss and 0.61 μmol/g.sec. corresponding CO₂ gain,while after the treatment, the powder gave 8.24 μmol/g.sec. maximum COloss and 3.29 μmol/g.sec. corresponding CO₂ gain.

[0037] Thus as shown, the high surface area molybdenum carbide catalystof the present invention is useful both in the methane dry reformingreaction as well as in the water gas shift reaction. The low temperaturei.e., 200° to 400° C. water gas shift reaction is very useful for fuelcell applications in which carbon monoxide reacts with water vapor togenerate hydrogen, a clean efficient energy source for fuel cells andcarbon dioxide, a harmless gas for fuel cells. The molybdenum carbidecatalyst of the present invention is excellent in this low temperatureapplication. This can be activated by an in-situ heat treatmentimmediately before use as a catalyst in the fuel cell by annealing ofthe catalyst in hydrogen, hydrogen carbon monoxide or hydrogen methanemixtures at 300° to 600° C. for 0.5 to 5 hours. Further, partiallyoxidized high surface area molybdenum carbide catalyst can bereactivated or recovered by similar in-situ re-carburization treatment.Again by annealing in hydrogen or hydrogen carbon monoxide or hydrogenmethane mixtures at temperatures of 400° to 700° C. for 0.5 to 5 hours.Thus, the present invention is extremely useful in fuel cellapplication.

This has been a description of the present invention along with thepreferred method of practicing the present invention. However, themethod itself should only be defined by the appended claims wherein weclaim:
 1. The method of forming hydrogen from a gas mixture of methaneand carbon dioxide comprising contacting gas said mixture with acatalyst comprising molybdenum carbide having a surface area of at least35 m²/g.
 2. The method claimed in claim 1 wherein said catalyst has asurface area of at least about 50 m²/g.
 3. The method claimed in claim 1wherein said gas mixture has a ratio of carbon dioxide to methane offrom about 1 to 10 to 10 to 1 by volume.
 4. The method claimed in claim3 wherein said reaction is conducted at a temperature of about 700° toabout 900° C.
 5. The method of conducting a water gas shift reactioncomprising contacting a gas comprising a mixture of hydrogen, carbonmonoxide and water vapor at a temperature of about 200° to 550° C. incontact with a catalyst said catalyst comprising molybdenum carbide. 6.The method claimed in claim 5 wherein said molybdenum carbide has asurface area greater than 35 m²/g.
 7. A method of utilizing a molybdenumcarbide catalyst in a reaction vessel having a controlled atmospherecomprising: passivating said molybdenum carbide catalyst to form oxideson surfaces of said molybdenum carbide catalyst; introducing saidmolybdenum carbide catalyst into a reaction vessel; activating saidmolybdenum carbide catalyst by passing a carburizing gas in contact withsaid catalyst at an elevated temperature effective to activate saidcatalyst.
 8. The method claimed in claim 7 further comprising passing acarbon containing gas in contact with said catalyst to form a reactionwhereby a said catalyst is at least partially deactivated; furthercomprising reactivating said catalyst by introducing a carburizing gasinto said reaction vessel in contact with said catalyst at a temperatureeffect to reactivate said catalyst.
 9. A method of forming a highsurface area Mo₂C comprising soaking a molybdenum compound selected fromthe group consisting of molybdates and oxide in a H/CO gas at 300°-400°C. for 1-5 hours; subsequently soaking said molybdenum compound in aH/CH₄ mixture for 3-5 hours at a temperature of 550°-850° C.